US20210376310A1 - Atomic layer deposition of ionically conductive coatings for lithium battery fast charging - Google Patents

Atomic layer deposition of ionically conductive coatings for lithium battery fast charging Download PDF

Info

Publication number
US20210376310A1
US20210376310A1 US17/333,485 US202117333485A US2021376310A1 US 20210376310 A1 US20210376310 A1 US 20210376310A1 US 202117333485 A US202117333485 A US 202117333485A US 2021376310 A1 US2021376310 A1 US 2021376310A1
Authority
US
United States
Prior art keywords
canceled
lithium
containing precursor
material particles
oxygen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
US17/333,485
Other languages
English (en)
Inventor
Neil P. Dasgupta
Kuan-Hung Chen
Eric Kazyak
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Michigan
Original Assignee
University of Michigan
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Michigan filed Critical University of Michigan
Priority to US17/333,485 priority Critical patent/US20210376310A1/en
Publication of US20210376310A1 publication Critical patent/US20210376310A1/en
Assigned to UNITED STATES DEPARTMENT OF ENERGY reassignment UNITED STATES DEPARTMENT OF ENERGY CONFIRMATORY LICENSE (SEE DOCUMENT FOR DETAILS). Assignors: UNIVERSITY OF MICHIGAN
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/4417—Methods specially adapted for coating powder
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/409—Oxides of the type ABO3 with A representing alkali, alkaline earth metal or lead and B representing a refractory metal, nickel, scandium or a lanthanide
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45529—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making a layer stack of alternating different compositions or gradient compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0409—Methods of deposition of the material by a doctor blade method, slip-casting or roller coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0428—Chemical vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This invention relates to electrochemical devices, such as lithium battery electrodes, thin film lithium batteries, and lithium batteries including these electrodes.
  • LIBs lithium-ion batteries
  • EVs electric vehicles
  • One of the primary factors limiting the fast charge ability of state-of-the-art LIBs is the tendency for plating out of metallic Li on the graphite electrode during charging. This phenomenon leads to rapid capacity fading of the cell, consumption of the electrolyte (cell drying), and the potential for short-circuit from dendrites penetrating the separator.
  • ALD Atomic Layer Deposition
  • SALD Spatial Atomic Layer Deposition
  • ALD films are promising for electrochemical storage systems for three dimensional (3D) battery architectures, porous electrode coatings, encapsulation, etc.
  • 3D three dimensional
  • These studies have fabricated a range of oxide, phosphate, and sulfide materials with a wide range of ionic conductivities (10 ⁇ 10 to 6 ⁇ 10 ⁇ 7 S/cm).
  • the highest reported ionic conductivity in ALD films is in LiPON films (3.7 ⁇ 10 ⁇ 7 S/cm in solid-state or 6.6 ⁇ 10 ⁇ 7 S/cm in liquid cell).
  • the present disclosure provides methods of making improved lithium-ion batteries having reduced tendency for plating out of metallic lithium on the graphite electrode during charging.
  • a surface coating is implemented on graphite particles or the post-calendered electrodes.
  • This coating may be a lithium borate-carbonate (LBCO) film deposited by atomic layer deposition (ALD).
  • LBCO lithium borate-carbonate
  • ALD atomic layer deposition
  • the film may conformally coat the graphite particles, due to the fact that ALD relies on self-limiting reactions and is not line-of-sight.
  • the film has previously been shown to exhibit ionic conductivities above 2 ⁇ 10 ⁇ 6 S/cm and excellent electrochemical stability.
  • the system and method for depositing this film on a solid-state-batteries as an interfacial layer or stand-alone solid-electrolyte are discussed in further details in U.S. Patent Application Publication No. 2020/0028208, which is incorporated by reference as if set forth in its entirety herein for all purposes.
  • the present disclosure demonstrates dramatic improvements to liquid-electrolyte-based lithium-ion battery performance by applying the LBCO ALD film to graphite electrodes, enabling fast-charging of high loading (>3 mAh/cm 2 ) electrodes in 15 minutes with minimal capacity fading.
  • the films used are also thinner than those proposed in U.S. Patent Application Publication No. 2020/0028208.
  • the present disclosure provides methods for forming an electrochemical device using an ALD.
  • a Li 3 BO 3 —Li 2 CO 3 (LBCO) film is produced using ALD.
  • the ALD LBCO film growth is self-limiting and linear over a range of deposition temperatures. The ability to tune the structure and properties of the film with deposition conditions and post-treatments is demonstrated for this film. Higher ionic conductivity than any previously reported ALD film (>10 ⁇ 6 S/cm at room temperature) with an ionic transference number of >0.9999 is achieved, and the film was shown to be stable over a wide range of potentials relevant for liquid-electrolyte-based batteries.
  • the present disclosure provides a method of making a film for an electrochemical device.
  • the method includes the steps of: (a) exposing a substrate to a lithium-containing precursor followed by an oxygen-containing precursor; and (b) exposing the substrate to a boron-containing precursor followed by the oxygen-containing precursor whereby a film is formed.
  • the electrochemical device can be a cathode or an anode.
  • the film can be comprised of boron, carbon, oxygen, and lithium.
  • step (a) can be continuously repeated between 1 and 10 times during a first subcycle and/or step (b) can be continuously repeated between 1 and 10 times during a second subcycle.
  • both the first subcycle and second subcycle can be repeated between 1 and 5000 times in a supercycle.
  • the lithium-containing precursor may comprise a lithium alkoxide.
  • the lithium-containing precursor may comprise lithium tert-butoxide.
  • the lithium-containing precursor can be selected from the group consisting of lithium tert-butoxide, tetramethylheptanedionate, lithium hexamethyldisilazide, and mixtures thereof.
  • the boron-containing precursor may comprise a boron alkoxide.
  • the boron-containing precursor may comprise triisopropylborate.
  • the boron-containing precursor may be selected from the group consisting of triisopropylborate, boron tribromide, boron trichloride, triethylboron, tris(ethyl-methylamino) borane, trichloroborazine, tris(dimethylamido)borane, trimethylborate, diboron tetrafluoride, and mixtures thereof.
  • the oxygen-containing precursor can be selected from the group consisting of ozone, water, oxygen plasma, ammonium hydroxide, oxygen, and mixtures thereof.
  • the oxygen-containing precursor comprises ozone.
  • the lithium-containing precursor, the boron-containing precursor, and the oxygen-containing precursor can be in a gaseous state.
  • the film can have a thickness of 0.1 to 50 nanometers.
  • the film can have an ionic conductivity of greater than 1.0 ⁇ 10 ⁇ 7 S/cm. Additionally, in the method, the film can have an ionic transference number of greater than 0.9999 from 0-6 volts vs lithium metal.
  • step (a) and step (b) can occur at a temperature between 50° C. and 280° C. In another embodiment of the method, step (a) and step (b) can occur at a temperature between 200° C. and 220° C. Additionally, in the method, step (a) and step (b) occur in the presence of ozone. In one embodiment, step (a) can occur before step (b), and in another embodiment, step (b) can occur before step (a).
  • the film can be annealed in a temperature range of 100° C. to 500° C. after step (a) and step (b).
  • This disclosure also provides a film formed by any embodiments of the method described above.
  • the present disclosure provides a method of making an electrochemical device.
  • the method includes the steps of: (a) exposing a substrate to a lithium-containing precursor followed by an oxygen-containing precursor; and (b) exposing the substrate to a boron-containing precursor followed by the oxygen-containing precursor, wherein an film can be formed on the substrate, and wherein the substrate can be selected from an anode or a cathode.
  • the substrate can be an anode.
  • the anode may comprise of a material selected from the group consisting of lithium metal, magnesium metal, sodium metal, zinc metal, graphite, lithium titanate, hard carbon, tin/cobalt alloy, silicon, silicon-carbon composites, transition-metal oxides, transition-metal sulfides, and transition-metal phosphides, soft carbon, and mixtures thereof.
  • the anode material can comprise graphite.
  • the substrate can be a cathode.
  • the substrate can be planar, and/or three dimensional, and/or corrugated. Additionally, in the method, the substrate can be a high-aspect-ratio three dimensional structure.
  • the film can be a film that is comprised of boron, carbon, oxygen, and lithium.
  • step (a) can be continuously repeated between 1 and 10 times in a first subcycle. Additionally, in the method, step (b) can be continuously repeated between 1 and 10 times in a second subcycle. The first subcycle and second subcycle can be repeated between 1 and 5000 times in a supercycle.
  • the lithium-containing precursor may comprise a lithium alkoxide.
  • the lithium-containing precursor can be selected from the group consisting of lithium tert-butoxide, tetramethylheptanedionate, lithium hexamethyldisilazide, and mixtures thereof.
  • the boron-containing precursor can comprise triisopropylborate.
  • the oxygen-containing precursor can be selected from the group consisting of ozone, water, oxygen plasma, ammonium hydroxide, oxygen, and mixtures thereof.
  • the oxygen-containing precursor can comprise ozone.
  • the lithium-containing precursor, the boron-containing precursor, and the oxygen-containing precursor can be in a gaseous state.
  • the film can have a thickness of 0.1 to 50 nanometers.
  • the film can have an ionic conductivity of greater than 1.0 ⁇ 10 ⁇ 7 S/cm. Additionally, in the method, the film can have an ionic transference number of greater than 0.9999 from 0-6 volts vs lithium metal.
  • step (a) and step (b) can occur at a temperature between 50° C. and 280° C. In another embodiment of the method, step (a) and step (b) can occur at a temperature between 200° C. and 220° C.
  • step (a) and step (b) can occur in the presence of ozone. Additionally, in the method, step (a) can occur before step (b). In another embodiment of the method, step (b) can occur before step (a).
  • the film can be amorphous.
  • the present disclosure covers the deposition of nanoscale lithium borate-based or lithium carbonate-based thin films onto electrode materials/particles (positive and/or negative electrode) to enable faster charging rates by reducing polarization, improving transport, and/or reducing/preventing lithium plating.
  • Negative electrode materials could include carbonaceous materials (graphite, soft carbon, hard carbon) and composites thereof, composites of graphite and Si, lithium titanate (LTO), lithium metal, etc.
  • Positive electrode materials could include NMC (111, 532, 622, 811, etc.), NCA, NMCA, LFP, LMO, LMNO, and composites thereof, etc.
  • the film could be deposited on electrodes after calendering (including binder and additives) or on powders before casting.
  • the present disclosure provides materials with high ionic conductivity (>1.0 ⁇ 10 ⁇ 7 S/cm at room temperature) and good electrochemical stability at low potentials vs. Li/Li+. Without intending to be bound by theory, at least three mechanisms may be involved with use of the film. i.e., the film could alter the wettability of the liquid electrolyte, the lithium metal, or alter the solid electrolyte interphase (SEI) composition and properties.
  • SEI solid electrolyte interphase
  • FIG. 1 is a schematic of a thin film lithium battery.
  • FIG. 2 depicts a process flowchart of a method of making a lithium borate-carbonate film.
  • FIG. 3 depicts cycling performance of graphite/NMC 532 coin cells with and without LBCO ALD coatings on the graphite electrodes, wherein (A) shows discharge capacity vs. cycle number, and wherein (B) shows Coulombic efficiency vs. cycle number, and wherein (C) shows Energy efficiency vs. cycle number.
  • FIG. 4 depicts the voltage profiles for cycle 10 of 4C fast-charge cycling, wherein (A) shows the charge voltage profile, and wherein (B) shows the discharge voltage profile along with dQ)/dV.
  • FIG. 5 depicts a demonstration of LBCO ALD coating approach for graphite electrodes.
  • A is a schematic of the electrode fabrication process including slurry-casting, calendaring, ALD, and cell assembly.
  • B,C are SEM images of a torn cross-section of LBCO 500x coated graphite electrode
  • D is an SEM image of focused-ion beam cross-section through a single graphite particle showing the conformal LBCO encapsulation of the particle.
  • E is an XPS survey scan and calculated composition of 250x LBCO-coated electrode surface.
  • FIG. 6 depicts SEI formation during a first preconditioning cycle.
  • A is a charge curve for first preconditioning cycle of graphite-NMC532 coin cells with varying thicknesses of the LBCO coating on the graphite electrode.
  • B is differential voltage curves corresponding to the SEI formation plateau in (A).
  • C is a schematic of the surface film evolution during preconditioning for control and LBCO 250x electrodes.
  • D is the composition of electrode surface at various stages of preconditioning as measured by XPS after 60 seconds of Ar sputtering to reduce adventitious species.
  • FIG. 7 depicts extended cycling of NMC532/graphite pouch cells with and without LBCO coating.
  • A is a discharge capacity for each cell over the first 100 fast-charge cycles and 3 capacity checks.
  • B is a discharge capacity for only periodic C/3 capacity-check cycles over 500 total fast-charge cycles. The 80% line is based on initial C/3 capacity check.
  • C is Coulombic efficiency values for fast-charge cycles in (A). Data points for the capacity checks and the subsequent fast-charge cycles were omitted due to changes in charge/discharge rates which cause unmeaningful CE values.
  • D is the discharge capacity for 4C fast-charge cycles only. The 80% line is based on initial fast-charge cycle.
  • (E) is a charge curve for first 4C charge
  • (F) is the same for 100 th 4C charge.
  • a constant current (CC) was applied until a cutoff voltage of 4.2 V, followed by a constant voltage (CV) hold until the total time for the charging step reached 15 minutes.
  • FIG. 8 depicts post mortem SEM images of graphite electrode cross-sections after 100 fast-charge cycles for (A) uncoated control and (B) LBCO 250x.
  • FIG. 9 depicts electrochemical impedance spectroscopy of graphite electrodes at various SOCs with/without LBCO ALD coating.
  • A is an equivalent circuit model that was used to fit the EIS spectra.
  • B is a stacked bar plot showing fitted resistance values for each resistance element of coated/uncoated electrodes at 3 different states of charge. Fitted resistances were multiplied by the area, 2.545 cm 2 to get area-specific resistances.
  • C is a schematic illustration of the origins of each circuit component in (A). Nyquist plots of uncoated control (D) and LBCO 250x (E) electrodes with selected frequencies labelled and marked by red dots and features labelled with their corresponding source based on the equivalent circuit model.
  • FIG. 10 depicts fast-charging and Li plating in 3-electrode cells.
  • A is graphite electrode potential vs. Li/Li+ during and after 4C fast charging of control and LBCO 250x electrodes.
  • B is an optical image of uncoated control graphite electrode cross-section after charging to 50% SOC at 4C in half cell.
  • C is the same for LBCO 250x electrode.
  • FIG. 11 depicts in (A), measured thickness of graphite electrodes after subtracting current collector thickness for control, heated control, and LBCO 250x.
  • (B) mass of punched electrode pieces for the same 3 treatments. Each mass/thickness measurement was taken on 5 separate areas and averaged. The error bars represent one standard deviation.
  • FIG. 12 depicts F 1 s core scans for control and LBCO 250x electrodes after dipping into electrolyte for 30 minutes and after charging to 4.2 V.
  • FIG. 13 depicts B 1 s core scans for LBCO 250x electrodes before (pristine) and after (Dip) dipping in LiPF 6 -based electrolyte. Both are after 120 s of Ar sputtering, removing surface species. No BE shifts are evident between the two spectra, and the binding energy value for the B 1 s of LBCO is consistent with our previous work (191.6 eV). This indicates that the LBCO film remains intact on the graphite surface after dipping.
  • FIG. 14 depicts Practical Effective Attenuation Length calculation for B 1 s photoelectrons excited by Al K ⁇ x-rays travelling through lithium fluoride. At the selected depth of 1.0 nm, the signal from the underlying film is attenuated to 74.6%, similar to the observed decrease in B 1 s signal after immersion of the LBCO-coated graphite in the electrolyte.
  • FIG. 15 depicts in (A), discharge capacity vs. cycle life for various electrode treatments.
  • discharge capacity is shown for various LBCO coating thicknesses at increasing charging rates. Cells were discharged at C/2 for all cycles,
  • FIG. 16 depicts charge and discharge curves for uncoated control and LBCO 250x pouch cells at C/10 showing similar behavior of both cells at low rates.
  • FIG. 17 depicts in (A), graphite electrode potential vs. Li/Li + during and after 4C fast charging of control and LBCO 250x electrodes; and in (B), Nyquist plots of control electrode at four points during the OCV step, as labelled in (A); and in (C), the same for LBCO 250x electrode.
  • the low-frequency region of the control changes significantly, whereas the LBCO-coated electrode impedance is stable throughout.
  • metal as used herein can refer to alkali metals, alkaline earth metals, lanthanoids, actinoids, transition metals, post-transition metals, metalloids, and selenium.
  • One embodiment of the invention provides a method for forming a cathode wherein the method comprises: (a) exposing cathode material particles to a lithium-containing precursor followed by an oxygen-containing precursor to form a coating on the cathode material particles; (b) forming a slurry comprising the coated cathode material particles; (c) casting the slurry on a surface to form a layer; and (d) calendering the layer to form the cathode.
  • step (a) may further comprise exposing the cathode material particles to a boron-containing precursor followed by the oxygen-containing precursor to form the coating on the cathode material particles.
  • Step (a) can occur at a temperature between 50° C. and 280° C.
  • the method may further comprise: (e) placing a side of a separator in contact with the cathode; and (f) placing an opposite side of the separator in contact with an anode to form an electrochemical cell.
  • the lithium-containing precursor can comprise a lithium alkoxide.
  • the boron-containing precursor can comprise a boron alkoxide.
  • the oxygen-containing precursor can be selected from the group consisting of ozone, water, oxygen plasma, ammonium hydroxide, oxygen, and mixtures thereof.
  • the lithium-containing precursor, the boron-containing precursor, and the oxygen-containing precursor can be in a gaseous state.
  • the cathode material particles can be selected from the group consisting of lithium metal oxides wherein the metal is one or more of aluminum, cobalt, iron, manganese, nickel, vanadium, and lithium-containing phosphates having a general formula LiMPO 4 wherein M is one or more of cobalt, iron, manganese, and nickel.
  • the coating can be a film having a thickness of 0.1 to 50 nanometers.
  • the coating can be a film having an ionic conductivity of greater than 1.0 ⁇ 10 ⁇ 7 S/cm.
  • the coating can be a film having an ionic transference number of greater than 0.9999 from 0-6 volts vs lithium metal.
  • the coating can be a film that is electrochemically stable at a Li+/Li 0 redox potential or less.
  • the coating can be a film that increases wettability of a liquid electrolyte on the cathode material particles.
  • the coating can be a film that alters a solid electrolyte interphase that forms as a result of the cathode material particles interacting with an electrolyte relative to a reference solid electrolyte interphase that forms as a result of the cathode material particles having no film interacting with the electrolyte.
  • step (a) may further comprise exposing the anode material particles to a boron-containing precursor followed by the oxygen-containing precursor to form the coating on the anode material particles.
  • Step (a) can occur at a temperature between 50° C. and 280° C.
  • the method can further comprise: (e) placing a side of a separator in contact with the anode; and (f) placing an opposite side of the separator in contact with a cathode to form an electrochemical cell.
  • the lithium-containing precursor can comprise a lithium alkoxide.
  • the boron-containing precursor can comprise a boron alkoxide.
  • the oxygen-containing precursor can be selected from the group consisting of ozone, water, oxygen plasma, ammonium hydroxide, oxygen, and mixtures thereof.
  • the lithium-containing precursor, the boron-containing precursor, and the oxygen-containing precursor can be in a gaseous state.
  • the anode material particles can be selected from the group consisting of graphite, soft carbon, hard carbon, silicon, silicon-carbon composites, lithium titanate (LTO), lithium metal, and mixtures thereof.
  • the anode material particles can comprise graphite.
  • the coating can be a film having a thickness of 0.1 to 50 nanometers.
  • the coating can be a film having an ionic conductivity of greater than 1.0 ⁇ 10 ⁇ 7 S/cm.
  • the coating can be a film having an ionic transference number of greater than 0.9999 from 0-6 volts vs lithium metal.
  • the coating can be a film that is electrochemically stable at a Li+/Li 0 redox potential or less.
  • the coating can be a film that increases wettability of a liquid electrolyte on the anode material particles.
  • the coating can be a film that alters a solid electrolyte interphase that forms as a result of the anode material particles interacting with an electrolyte relative to a reference solid electrolyte interphase that forms as a result of the anode material particles having no film interacting with the electrolyte.
  • Another embodiment of the invention provides a method for forming a cathode for an electrochemical device, wherein the method comprises: (a) forming a mixture comprising cathode material particles; (b) calendering the mixture such that a porous structure is formed; and (c) exposing the porous structure to a lithium-containing precursor followed by an oxygen-containing precursor to form a coating on the porous structure.
  • Step (c) may further comprise exposing the porous structure to a boron-containing precursor followed by the oxygen-containing precursor to form the coating on the porous structure.
  • Step (c) can occur at a temperature between 50° C. and 280° C.
  • the method may further comprise: (d) placing a side of a separator in contact with the cathode; and (e) placing an opposite side of the separator in contact with an anode to form an electrochemical cell.
  • the lithium-containing precursor comprises a lithium alkoxide.
  • the boron-containing precursor comprises a boron alkoxide.
  • the oxygen-containing precursor can be selected from the group consisting of ozone, water, oxygen plasma, ammonium hydroxide, oxygen, and mixtures thereof.
  • the lithium-containing precursor, the boron-containing precursor, and the oxygen-containing precursor can be in a gaseous state.
  • the cathode material particles can be selected from the group consisting of lithium metal oxides wherein the metal is one or more of aluminum, cobalt, iron, manganese, nickel, vanadium, and lithium-containing phosphates having a general formula LiMPO 4 wherein M is one or more of cobalt, iron, manganese, and nickel.
  • the coating can be a film having a thickness of 0.1 to 50 nanometers.
  • the coating can be a film having an ionic conductivity of greater than 1.0 ⁇ 10 ⁇ 7 S/cm.
  • the coating can be a film having an ionic transference number of greater than 09999 from 0-6 volts vs lithium metal.
  • the coating can be a film that is electrochemically stable at a Li + /LiF 0 redox potential or less.
  • the coating can be a film that increases wettability of a liquid electrolyte on the cathode material particles.
  • the coating can be a film that alters a solid electrolyte interphase that forms as a result of the cathode material particles interacting with an electrolyte relative to a reference solid electrolyte interphase that forms as a result of the cathode material particles having no film interacting with the electrolyte.
  • Another embodiment of the invention provides a method for forming an anode for an electrochemical device, wherein the method comprises: (a) forming a mixture comprising anode material particles; (b) calendering the mixture such that a porous structure is formed; and (c) exposing the porous structure to a lithium-containing precursor followed by an oxygen-containing precursor to form a coating on the porous structure.
  • Step (a) may further comprise exposing the porous structure to a boron-containing precursor followed by the oxygen-containing precursor to form the coating on the anode material particles.
  • Step (c) can occur at a temperature between 50° C. and 280° C.
  • the method may further comprise: (d) placing a side of a separator in contact with the anode; and (e) placing an opposite side of the separator in contact with a cathode to form an electrochemical cell.
  • the lithium-containing precursor may comprise a lithium alkoxide.
  • the boron-containing precursor may comprise a boron alkoxide.
  • the oxygen-containing precursor can be selected from the group consisting of ozone, water, oxygen plasma, ammonium hydroxide, oxygen, and mixtures thereof.
  • the lithium-containing precursor, the boron-containing precursor, and the oxygen-containing precursor can be in a gaseous state.
  • the anode material particles can be selected from the group consisting of graphite, soft carbon, hard carbon, silicon, silicon-carbon composites, titanate (LTO), lithium metal, and mixtures thereof.
  • the anode material particles can comprise graphite.
  • the coating can be a film having a thickness of 0.1 to 50 nanometers.
  • the coating can be a film having an ionic conductivity of greater than 1.0 ⁇ 10 ⁇ 7 S/cm.
  • the coating can be a film having an ionic transference number of greater than 0.9999 from 0-6 volts vs lithium metal.
  • the coating can be a film that is electrochemically stable at a Li + /Li 0 redox potential or less.
  • the coating can be a film that increases wettability of a liquid electrolyte on the anode material particles.
  • the coating can be a film that alters a solid electrolyte interphase that forms as a result of the anode material particles interacting with an electrolyte relative to a reference solid electrolyte interphase that forms as a result of the anode material particles having no film interacting with the electrolyte.
  • cathode for an electrochemical device, wherein the cathode comprises: cathode material particles selected from the group consisting of lithium metal oxides wherein the metal is one or more of aluminum, cobalt, iron, manganese, nickel, vanadium, and lithium-containing phosphates having a general formula LiMPO 4 wherein M is one or more of cobalt, iron, manganese, and nickel; and a nanoscale film on at least a portion of a surface of the cathode material particles, the film comprising a lithium borate-based material, or a lithium carbonate based material or a mixture thereof.
  • cathode material particles selected from the group consisting of lithium metal oxides wherein the metal is one or more of aluminum, cobalt, iron, manganese, nickel, vanadium, and lithium-containing phosphates having a general formula LiMPO 4 wherein M is one or more of cobalt, iron, manganese, and nickel
  • a nanoscale film on at least a portion of a surface
  • the cathode may further comprise: a separator in contact with the cathode; and an anode in contact with an opposite side of the separator to form an electrochemical cell.
  • the film can comprise Li 3 BP 3 —Li 2 CO 3 .
  • the film can have a thickness of 0.1 to 50 nanometers.
  • the film can have an ionic conductivity of greater than 1.0 ⁇ 10 ⁇ 7 S/cm.
  • the film can have an ionic transference number of greater than 0.9999 from 0-6 volts vs lithium metal.
  • the film can be electrochemically stable at a Li + /Li 0 redox potential or less.
  • the film can increase wettability of a liquid electrolyte on the cathode material particles.
  • the film can alter a solid electrolyte interphase that forms as a result of the cathode material particles interacting with an electrolyte relative to a reference solid electrolyte interphase that forms as a result of the cathode material particles having no film interacting with the electrolyte.
  • an anode for an electrochemical device wherein the anode comprises: anode material particles selected from the group consisting of graphite, soft carbon, hard carbon, silicon, silicon-carbon composites, lithium titanate (LTO), lithium metal, and mixtures thereof; and a nanoscale film on at least a portion of a surface of the anode material particles, the film comprising a lithium borate-based material, or a lithium carbonate based material or a mixture thereof.
  • the anode can further comprise: a separator in contact with the anode; and a cathode in contact with an opposite side of the separator to form an electrochemical cell.
  • the film can comprise Li 3 BO 3 —Li 2 CO 3 .
  • the film can have a thickness of 0.1 to 50 nanometers.
  • the film can have an ionic conductivity of greater than 1.0 ⁇ 10 ⁇ 7 S/cm.
  • the film can have an ionic transference number of greater than 09999 from 0-6 volts vs lithium metal.
  • the film can be electrochemically stable at a Li + /Li 0 redox potential or less.
  • the anode material particles can comprise graphite.
  • the film can increase wettability of a liquid electrolyte on the anode material particles.
  • the film can alter a solid electrolyte interphase that forms as a result of the anode material particles interacting with an electrolyte relative to a reference solid electrolyte interphase that forms as a result of the anode material particles having no film interacting with the electrolyte.
  • the lithium-ion battery can be a solid-state-battery or a liquid-electrolyte-based lithium-ion battery.
  • atomic layer deposition can be used in forming a thin film lithium battery 110 as depicted in FIG. 1 .
  • the thin film lithium battery 110 includes a current collector 112 (e.g., aluminum) in contact with a cathode 114 .
  • the separator 116 is arranged between the cathode 114 and an anode 118 , which is in contact with a current collector 122 (e.g., aluminum).
  • the current collectors 112 and 122 of the thin film lithium battery 110 may be in electrical communication with an electrical component 124 .
  • the electrical component 124 could place the thin film lithium battery 110 in electrical communication with an electrical load that discharges the battery or a charger that charges the battery.
  • the electrolyte for the battery 110 may be a liquid electrolyte.
  • the liquid electrolyte of the electrochemical cell may comprise a lithium compound in an organic solvent.
  • the lithium compound may be selected from LiPF 6 , LiBF 4 , LiClO 4 , lithium bis(fluorosulfonyl)imide (LiFSI), LiN(CF 3 SO 2 ) 2 (LiTFSI), and LiCF 3 SO 3 (LiTf).
  • the organic solvent may be selected from carbonate based solvents, ether based solvents, ionic liquids, and mixtures thereof.
  • the carbonate based solvent may be selected from the group consisting of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, methylethyl carbonate, ethylene carbonate, propylene carbonate, and butylene carbonate; and the ether based solvent is selected from the group consisting of diethyl ether, dibutyl ether, monoglyme, diglyme, tetraglyme, 2-methyltetrahydrofuran, tetrahydrofuran, 1,3-dioxolane, 1,2-dimethoxyethane, and 1,4-dioxane.
  • the first current collector 112 and the second current collector 122 can comprise a conductive metal or any suitable conductive material.
  • the first current collector 112 and the second current collector 122 comprise aluminum, nickel, copper, combinations and alloys thereof.
  • the first current collector 112 and the second current collector 122 have a thickness of 0.1 microns or greater. It is to be appreciated that the thicknesses depicted in FIG. 1 are not drawn to scale, and that the thickness of the first current collector 112 and the second current collector 122 may be different.
  • a suitable active material for the cathode 114 of the thin film lithium battery 110 is a lithium host material capable of storing and subsequently releasing lithium ions.
  • An example cathode active material is a lithium metal oxide wherein the metal is one or more aluminum, cobalt, iron, manganese, nickel and vanadium.
  • Non-limiting example lithium metal oxides are LiCoO 2 (LCO), LiFeO 2 , LiMnO 2 (LMO), LiMn 2 O 4 , LiNiO 2 (LNC)), LiNi x Co y O 2 , LiMn x Co y O 2 , LiMn x Ni y O 2 , LiMn x Ni y O 4 , LiNi x Co y Al z O 2 , LiNi 1/3 Mn 1/3 Co 1/3 O 2 and others.
  • LCO LiCoO 2
  • LiFeO 2 LiMnO 2
  • LiMn 2 O 4 LiNiO 2 (LNC)
  • LiNi x Co y O 2 LiMn x Co y O 2
  • LiMn x Ni y O 2 LiMn x Ni y O 4
  • LiNi x Co y Al z O 2 LiNi 1/3 Mn 1/3 Co 1/3 O 2 and others.
  • cathode active materials is a lithium-containing phosphate having a general formula LiMPO 4 wherein M is one or more of cobalt, iron, manganese, and nickel, such as lithium iron phosphate (LFP) and lithium iron fluorophosphates.
  • M is one or more of cobalt, iron, manganese, and nickel
  • LFP lithium iron phosphate
  • V 2 O 5 Another example of a cathode active material.
  • Many different elements, e.g., Co, Mn, Ni, Cr, Al, or Li may be substituted or additionally added into the structure to influence electronic conductivity, ordering of the layer, stability on delithiation and cycling performance of the cathode materials.
  • the cathode active material can be a mixture of any number of these cathode active materials.
  • a suitable material for the cathode 114 of the thin film lithium battery 110 is porous carbon (for a lithium air battery), or a sulfur containing material (for a lithium sulfur battery).
  • a suitable active material for the anode 118 of the thin film lithium battery 110 consists of lithium metal.
  • an example anode 118 material consists essentially of lithium metal.
  • a suitable anode 118 consists essentially of magnesium, sodium, or zinc metal.
  • a suitable anode 118 comprises a material selected from graphite, lithium titanate, hard carbon, tin/cobalt alloy, silicon, and silicon-carbon composites.
  • a suitable anode 118 comprises a conversion-type anode material such as a transition-metal oxide, a transition-metal sulfide, or a transition-metal phosphide.
  • the thin film lithium battery 110 comprises a separator 116 located between the cathode 114 and the anode 118 .
  • An example separator 116 material for the thin film lithium battery 110 can a permeable polymer such as a polyolefin.
  • Example polyolefins include polyethylene, polypropylene, and combinations thereof.
  • the separator 116 may have a thickness in the range of 1 to 200 nanometers, or in the range of 40 to 1000 nanometers.
  • FIG. 2 depicts a process flowchart 300 for a method of making an ionically conductive film using an atomic layer deposition process of the present invention.
  • the method can comprise a first step in which a substrate is exposed to a lithium-containing precursor, which reacts with the surface and the excess and product species are removed from the surface. Subsequently, an oxygen-containing precursor is exposed to the surface, and another reaction occurs.
  • another subcycle where a boron-containing precursor is exposed to the substrate followed by an oxygen-containing precursor can be repeated y times, where y may be any integer from 1 to 10.
  • This entire “supercycle” can then be repeated z times to deposit a layer of the desired thickness.
  • the value of z may be an integer between 1 and 5000, between 10 and 1000, or between 100 and 500.
  • This process may result in the formation of a film comprising lithium, boron, and oxygen, and in some cases carbon.
  • the precursors may be in a gaseous state.
  • the subcycles may occur in either order to start the supercycle.
  • the sequential reactions can be separated either chronologically or spatially.
  • the lithium-containing precursor may be selected from the group consisting of lithium tert-butoxide (LiO t Bu), 2,2,6,6-tetramethyl-3,5-heptanedionate (Li(thd)), and lithium hexamethyldisilazide (LiHMDS).
  • the lithium-containing precursor may be a lithium alkoxide such as lithium tert-butoxide.
  • the boron-containing precursor may be selected from the group consisting of triisopropylborate (TIB), boron tribromide (BBr 3 ), boron trichloride (BCl 3 ), triethylboron (TEB), tris(ethyl-methylamino) borane, trichloroborazine (TCB), tris(dimethylamido)borane (TDMAB); trimethylborate (TMB), diboron tetrafluoride (B 2 F 4 ).
  • the boron-containing precursor may be a boron alkoxide such as triisopropylborate.
  • the oxygen-containing precursor may be selected from the group consisting of ozone (O 3 ), water (H 2 O), oxygen plasma (O 2 (p)), ammonium hydroxide (NH 4 OH), Oxygen (O 2 ).
  • the oxygen-containing precursor may be ozone.
  • the film formed by the method 300 may have a thickness between 20 and 100 nanometers, between 0.1 and 1000 nanometers, between 1 and 100 nanometers, between 20 and 80 nanometers, or between 0.1 and 50 nanometers, or between 0.1 and 35 nanometers.
  • the ionically conductive film layer may have a total area specific-resistance (ASR) of less than 450 ohm cm 2 , or is less than 400 ohm cm 2 , or is less than 350 ohm cm 2 , or is less than 300 ohm cm 2 , or is less than 250 ohm cm 2 , or is less than 200 ohm cm 2 , or is less than 150 ohm cm 2 , or is less than 100 ohm cm 2 , or is less than 75 ohm cm 2 , or is less than 50 ohm cm 2 , or is less than 25 ohm cm 2 , or is less than 10 ohm cm 2 , or less than 5 ⁇ -cm 2 .
  • ASR total area specific-resistance
  • the film formed by the method 300 may have an ionic conductivity of greater than 1.0 ⁇ 10 ⁇ 7 S/cm, or greater than 1.0 ⁇ 10 ⁇ 6 S/cm, or greater than 1.5 ⁇ 10 ⁇ 6 S/cm, or greater than 2.0 ⁇ 10 ⁇ 6 &cm, or greater than 2.2 ⁇ 10 ⁇ 6 S/cm at standard temperature and pressure.
  • the ionically conductive layer may have an ionic transference number of greater than 0.9999 from 0-6 volts vs lithium metal.
  • the first step and second step may occur in any order and at a temperature between 50° C. and 280° C., or between 180° C. and 280° C., or between 200° C. and 220° C.
  • the substrate of the method of 300 can be an anode or a cathode.
  • the substrate of the method of 300 can be planar or have a three dimensional structure, such as a corrugated structure.
  • the present disclosure relates to forming an electrode for use in an electrochemical device, such as a lithium ion battery or a lithium metal battery.
  • the method for forming an electrode includes depositing a film of the present disclosure on a powdered electrode material, and forming a slurry comprising the coated electrode material. The slurry is then cast on a surface to form a layer, and the layer is dried and calendered to form the electrode.
  • the electrode material may be any of the anode materials or cathode materials described above.
  • the electrode may be produced by forming a slurry comprising an electrode material, casting the slurry on a surface to form a layer, and drying and calendering the layer. A film of the present disclosure is then deposited on a surface of the dried and calendered layer to form a thin film to complete forming the electrode.
  • the electrode may be produced by forming a slurry comprising an electrode material, casting the slurry on a surface to form a layer, calendering the layer, and depositing a film of the present disclosure on the layer. The film coated layer is then dried and calendered to complete forming the electrode.
  • the slurry as described in any of the preceding embodiments may be formed by mixing the electrode material or coated electrode material with an aqueous or organic solvent.
  • Suitable solvents may include N-methyl-2-pyrrolidone (NMP) or other suitable alternatives that would be readily understood to those skilled in the art.
  • NMP N-methyl-2-pyrrolidone
  • a binder may also be added to the slurry, such as polyvinylidene fluoride (PVDF) or any suitable alternative that would be readily understood to those skilled in the art.
  • PVDF polyvinylidene fluoride
  • a conductive additive such as a metallic powder or carbon black, may also be added to the slurry.
  • the layer of the electrode as discussed in any of the preceding embodiments may be dried and calendered to have a thickness that ranges between 1 to 200 microns. In some embodiments, the thickness of the electrode is less than 175 microns, or less than 150 microns, or less than 125 microns, or less than 100 microns, or less than 75 microns, or less than 50 microns.
  • the thin film coating on the surfaces of the electrode material as discussed in any of the preceding embodiments may have a thickness that ranges from 0.1 to 50 nanometers,
  • One example thin film coating comprises Li 3 BO 3 —Li 2 CO 3 .
  • control and baked control exhibit a larger polarization compared to the cells with LBCO coated graphite, and a characteristic peak and plateau associated with plating of metallic Li on the graphite electrode.
  • the decreased Li plating on the LBCO coated electrodes is corroborated by the absence of the Li reintercalation feature in the beginning of the discharge profile and the corresponding peak in the dQ/dV curve.
  • the proposed mechanism of these improvements is related to one or more of the following factors: (1) improved wettability of the liquid electrolyte on the electrode surface, enabling improved transport of Li ions into the electrode, reducing concentration gradients, (2) the LBCO film serves as an artificial solid electrolyte interphase (SEI), which reduces the amount of Li consumed in the first charging cycle, reduces the impedance of the SEI, and improves interfacial kinetics, (3) reducing the wettability of Li metal on the electrode surface, increasing the overpotential required to nucleate Li plating.
  • SEI solid electrolyte interphase
  • ALD has been scaled-up for roll-to-roll processing for other applications, and is already being used to coat lithium ion battery electrodes with other materials, it is possible to scale-up this technique.
  • the treatment can enable faster charging for a given electrode loading (as shown), or enable the use of thicker electrodes with higher loading, both of which are of great interest to commercial applications.
  • Enabling fast-charging ( ⁇ 4C) of lithium-ion batteries is an important challenge to accelerate the adoption of electric vehicles.
  • the desire to maximize energy density has driven the use of increasingly thick electrodes, which hinders power density.
  • atomic layer deposition was used to coat a single-ion conducting solid electrolyte (Li 3 BO 3 —Li 2 CO 3 ) onto post-calendered graphite electrodes, forming an artificial solid-electrolyte interphase (SEI).
  • the solid electrolyte coating When compared to uncoated control electrodes, the solid electrolyte coating: (1) eliminates natural SEI formation during preconditioning; (2) decreases interphase impedance by >75% compared to the natural SEI; and (3) extends cycle life 40-fold under 4C charging conditions, enabling retention of 80% capacity after 500 cycles in pouch cells with >3 mAh-cm ⁇ 2 loading.
  • Example 2 demonstrates that 4C charging without Li plating can be achieved through purely interfacial modification without sacrificing energy density, and sheds new light on the role of the SEI in Li plating and fast-charge performance.
  • Lithium-ion batteries have become a vital part of the way that society stores and uses electrical energy.
  • EVs electric vehicles
  • ALD affords unparalleled control of film thickness and conformality owing to the self-limiting nature of the surface reactions.
  • ALD is a powerful means of interface modification for electrode materials in LIBs, [Refs. 31 - 40 ] but work to date has largely focused on coating cathodes to improve interface stability.
  • [Refs. 41 - 43 ] Reports of coatings on graphite have been limited to Al 2 O 3 [Refs. 31 , 32 , 34 , 44 ] and TiO 2 , [Refs. 33 , 44 ] and have generally been extremely thin, often less than 1 nm. This is due to the fact that these oxide materials are relatively poor ionic conductors, even after they are electrochemically lithiated, which consumes Li.
  • FIG. 5 in (B) shows an XPS survey scan of a graphite electrode surface coated with 250 ALD supercycles of LBCO ( ⁇ 20 nm).
  • One supercycle consists of sequential exposures of lithium Cert-butoxide, ozone, triisopropylborate, and ozone, each separated by purging, as described previously.
  • This will be termed LBCO 250x throughout Example 2, and other thicknesses will be described similarly based on the number of ALD cycles.
  • the surface is composed of lithium, carbon, boron, and oxygen, [Ref. 29 ]
  • FIG. 5 A high-magnification image of a focused-ion beam (FIB) cross-section is shown in (D) of FIG. 5 ,
  • the film is ⁇ 40 nm thick, as expected for the 500x coating, and conformally coats along the entire surface of the graphite particle, including re-entrant surface geometries and the bottom surface that would be shadowed when using line-of-sight deposition methods.
  • This type of conformal coating with precisely controllable thickness would be challenging to achieve with other coating techniques, demonstrating the unique properties of ALD for coating of porous materials.
  • the thickness and mass of multiple control (no exposure to the ALD chamber), heated control, and LBCO 250x coated electrodes were measured.
  • the heated control was exposed to the temperature and pressure conditions of the ALD reactor for the same length of time as the 250x process.
  • a table of the resulting measurements is shown in Table 1, which indicates that the total thickness of the calendared graphite electrodes increased by approximately 4-8% due to the ALD temperature and pressure conditions.
  • Graphite electrodes (3.18 mAh-cm ⁇ 2 loading, details in Experimental Methods) were prepared with varying numbers of ALD cycles (50x, 250x, and 500x corresponding to 4, 20, and 40 nm) to investigate the impact of the ALD coating on cell performance and identify the optimum thickness. These electrodes were assembled into coin cells with NMC532 cathodes for testing (details in Experimental Methods). After assembly, the cells were preconditioned with (3) C/10 constant current (CC) cycles, the first of which is shown in (A) of FIG. 6 .
  • CC constant current
  • the first plateau in the first charge (observed at ⁇ 3.0 volts) is associated with the initial SEI that forms on the graphite surface as the potential of the electrode drops below the reductive stability limit of the electrolyte. [Refs. 24 , 46 ]
  • This plateau which appears as a peak in the dQ/dV plot ((B) in FIG. 6 ), decreases with increasing thickness of LBCO coating.
  • the plateau is almost completely suppressed in the 250x sample, and is absent in the 500x sample. This indicates that when the LBCO coating is sufficiently thick, it passivates the surface of the graphite and prevents reductive side-reactions with the salt and solvents that lead to SEI formation and growth.
  • the control electrode was still comprised of >90% carbon, with a modest increase in the amount of fluorine present.
  • Examination of the F 1 s core scan ( FIG. 12 ), reveals that this F content arises from residual LiPF 6 salt, rather than a reacted interphase.
  • the 250x LBCO electrode exhibited a greater increase in F content, most of which was LiF in character based on the core scans. This indicates that the LBCO ALD film chemically reacts with the ions in the electrolyte under open circuit conditions. In the future, computational studies would be valuable to further elucidate this mechanism.
  • the 250x LBCO electrode surface composition was nearly identical to the dipped sample, while the control electrode changed dramatically.
  • the carbon content of the control decreased from 92% to 32%, while the Li content increased from nearly zero to 37%, the O increased from near zero to 20%, and the F increased from 5% to 10%.
  • the improved electrochemical stability of the 250x LBCO electrode compared to the control is consistent with the voltage curve analysis in (A) and (B) of FIG. 6 . This is also consistent with cyclic voltammetry data for ALD LBCO, which do not show reductive currents as the electrode potential is decreased within the range of natural SEI formation. [Ref. 29 ] This illustrates the benefits of using a solid-state electrolyte with a wide electrochemical stability window to provide several of the properties of an ideal a-SEI.
  • single-layer pouch cells 70 cm 2 electrodes were fabricated for the control and the optimal 250x LBCO coating.
  • Extended cycling with 4C fast charging was performed, following the U.S. Department of Energy test protocol for fast charging.
  • the accessible capacity at low charge rate was also checked every 50 cycles.
  • the control cells exhibit rapid capacity fading in the first 10-20 cycles before reaching a more stable aging condition.
  • the rapid capacity fade in the initial cycles of the control corresponds to a dip in the Coulombic efficiency (CE), which has been shown to be a result of Li plating.
  • CE Coulombic efficiency
  • the capacity retention at C/3 is 67.3% after 50 4C-charge cycles.
  • the CE of the LBCO 250x cell is consistently higher than the control, and does not exhibit the initial dip in CE.
  • the LBCO 250x cell exhibits much less capacity fade, retaining 89.5% of the original capacity to 50 cycles, and 79.4% after 500 cycles ((B) in FIG. 7 ).
  • the plot in (D) of FIG. 7 shows only the cycles with 4C fast-charging (without the capacity checks). Compared to the accessible capacity of the initial 4C charge cycle, the control cell fades to 80% capacity after only 12 cycles. In comparison, the LBCO 250x retains more than 80% throughout the 500-cycle test. This represents a greater than 40-fold increase in cycle life.
  • the most substantial difference between the control and coated electrode is that the LBCO 250x has a significantly lower SEI resistance (R SEI ) than the control (4.1 ⁇ -cm 2 vs. 17.3-17.8 ⁇ -cm 2 ).
  • R SEI SEI resistance
  • This decreased SEI impedance can be rationalized by the facts that: (1) the LBCO coating successfully suppressed natural SEI formation during charging; and (2) the LBCO a-SEI has higher ionic conductivity than the natural SEI assuming that the natural SEI is of similar thickness, which is supported by previous reports. [Ref. 55 ]
  • the lower R SEI reduces overall cell polarization, consistent with (E) in FIG. 7 .
  • FIG. 10 shows the electrode potential during 4C charging at a constant current to approximately 50% of the theoretical electrode capacity, followed by a rest period during which periodic EIS spectra were collected.
  • the voltage curves are substantially different for the control and LBCO 250x electrodes.
  • the control electrode potential (orange) quickly decreases to a negative potential, reaches a local minimum, and then begins increasing towards 0 V vs Li/Li+ before reaching a plateau.
  • the LBCO 250x electrode decreases more slowly, and does not reach a local minimum within the duration of the fast-charging.
  • the SOC distribution and Li plating on the graphite electrodes were visualized using ex situ optical microscopy. Similar to the 3-electrode cells, 2-electrode half-cells were charged at a 4C rate to 50% SOC. They were then immediately disassembled (within 1 minute) and imaged to observe the amount of Li plating and the gradient in SOC through the thickness before the open-circuit rest period.
  • Example 2 demonstrated the use of ALD to deposit a stable and ionically-conductive a-SEI on graphite, and demonstrated the impact of this coating on fast-charging performance.
  • Electrode Fabrication Graphite and NMC electrodes were fabricated using the pilot scale roll-to-roll battery manufacturing facilities at the University of Michigan Battery Lab, as reported previously. [Ref. 9 ] The graphite electrodes were fabricated with a total loading of 9.40 mg-cm ⁇ 2 including 94% natural graphite (battery grade, SLC1506T, Superior Graphite), 1% C65 conductive additive, and 5% CMC/SBR binder), resulting in a theoretical capacity of 3.18 mAh-cm ⁇ 2 . The electrodes were calendered to a porosity of ⁇ 32%. After coating, drying; calendaring, and punching, the full electrodes were moved into a Savannah S200 ALD reactor integrated into an argon glovebox for coating.
  • LiNi 0.5 Mn 0.3 Co 0.2 O 2 (battery grade, NMC-532, Toda America) was used as the cathode material.
  • the cathode formulation was 92 wt. % NMC-532, 4 wt. % C65 conductive additive, and 4 wt. % PVDF binder.
  • the cathode slurry was cast onto aluminum foils (15 ⁇ m thick) with a total areal mass loading of 16.58 mg-cm ⁇ 2 and then calendered to 35% porosity. This yields an N:P ratio of 1.1-1.2.
  • the LBCO ALD film was deposited onto the electrodes using a modified version of the previously reported ALD process.
  • This process uses lithium tert-butoxide, triisopropyl borate, and ozone precursors.
  • the lithium Cert-butoxide pulse length was increased to 10 seconds, with a 20 seconds exposure
  • the triisopropyl borate pulse was increased to 0.25 seconds, with 20 seconds exposure.
  • a Woollam M-2000 was used to collect data, which were then fit with a Cauchy layer on top of the native oxide of the Si, Film composition was characterized with X-ray photoelectron spectroscopy (XPS) using a Kratos Axis Ultra with monochromated Al K ⁇ source. The XPS system is directly connected to an argon (Ar) glovebox to avoid all air exposure of samples. XPS data was analyzed with CasaXPS. Binding energies were calibrated using the C-C peak in the C 1 s core scan at 284.8 eV. Film and electrode morphology were characterized by scanning electron microscopy using a Helios 650 nanolab dual beam SEM/FIB system. Electrode masses were measured using a Pioneer-series balance [Ohaus] inside an Argon glovebox, and electrode thicknesses were measured using an electronic thickness gauge ( 547 - 400 S, Mitutoyo).
  • Pouch cell electrodes (7 cm ⁇ 10 cm) were punched and assembled into single-layer pouch cells in a dry room ( ⁇ 40° C. dewpoint) at the University of Michigan Battery Laboratory. Each pouch cell consisted of an anode, a cathode, and a polymer separator (12 ⁇ m ENTEK). A NIP ratio of ⁇ 1.2 was fixed for all pouch cells. Assembled dry cells were first baked in vacuum ovens at 50° C. overnight to remove residual moisture prior to electrolyte filling. 1 M LiPF 6 in 3/7 EC/EMC with 2% VC (SoulBrain MI) was used as the electrolyte.
  • pouch cells were vacuum-sealed and rested for 24 hours to allow for electrolyte wetting. Subsequently, two formation cycles were performed at C/20 and C/10 rates (one cycle for each C-rate). After formation, cells were transferred back into the dry room, degassed, and then re-sealed prior to subsequent cycling.
  • Electrochemical Characterization Electrochemical impedance spectroscopy (EIS) was performed using an SP-200 or VSP potentiostat (Bio-logic USA). The spectra were fit to the equivalent circuit shown in FIG. 9 using the RelaxIS 3® software suite (rhd instruments GmbH & Co. KG), 3-electrode measurements were performed using a commercial electrochemical test cell (ECC-PAT-Core, EL-CELL GmbH) with a Li metal ring reference electrode. Preconditioning, rate tests, and fast-charge cycling were performed using a Maccor series 4000 cell cycler.
  • EIS Electrochemical impedance spectroscopy
  • Post-mortem Characterization XPS after preconditioning was performed as listed above. Scanning electron microscopy and focused-ion beam miffing was performed on a Helios G4 PFIB UXe (Thermo Fisher), The coin cells used for (B) & (C) in FIG. 10 were disassembled using a disassembly die (MTI Corp.) as soon as possible after fast-charging was completed (within 1 minute). The electrodes were immediately rinsed in dimethyl carbonate to remove residual electrolyte and halt Li transport through the liquid phase. The electrodes were torn to create a cross-section, and then imaged with a VHX-7000 digital microscope (Keyence Corp.).
  • Thickness-dependent cycling performance of coin cells The 250x and 500x LBCO coated cells exhibited significantly improved rate capability and capacity retention compared to the control ( FIG. 15 ).
  • the LBCO 50x cell was initially better than the control, but during extended cycling, eventually converged with the controls. This is consistent with the observation in (A) & (B) of FIG. 6 that the 50x coating was not sufficient to passivate the electrode surface.
  • the heated control exhibited similar cycling performance to the unheated controls. Therefore, the observed differences in behavior are attributed to the coating itself, rather than the processing conditions.
  • the circuit elements used to fit graphite electrodes typically include: (1) a resistance (R series ) associated with the ohmic drop; (2) a resistance (R P_CC ) associated with the contact between the graphite particles and between the graphite and the current collector; (3) a resistance (R SEI ) associated with ionic transport through the SEI; (4) a resistance (R CT ) associated with charge transfer processes; and (5) a diffusion element associated with solid-state diffusion within the graphite particles.
  • R P-CC , R SEI , and R CT each have a capacitance associated with them.
  • Constant phase elements were used for fitting R P-CC and R CT to account for the suppressed semi-circles that are observed.
  • a Hucun-Negarni (HN) term [Ref. 63 ] was used in conjunction with the SEI resistance to capture the asymmetry of the SEI impedance feature in the spectra. This asymmetry has been observed previously, [Ref. 54 ] and is generally accounted for by incorporating either a transmission line model or an HN element. It arises due to the combination of ionic transport through the SEI layer and the electrochemical reactions occurring at the surface of the SEI.
  • the present invention provides a method for forming an electrode wherein a film is coated on electrode material particles or post-calendered electrodes.
  • This coating may be a lithium borate-carbonate film deposited by atomic layer deposition.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
US17/333,485 2020-05-29 2021-05-28 Atomic layer deposition of ionically conductive coatings for lithium battery fast charging Pending US20210376310A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US17/333,485 US20210376310A1 (en) 2020-05-29 2021-05-28 Atomic layer deposition of ionically conductive coatings for lithium battery fast charging

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202063032205P 2020-05-29 2020-05-29
US17/333,485 US20210376310A1 (en) 2020-05-29 2021-05-28 Atomic layer deposition of ionically conductive coatings for lithium battery fast charging

Publications (1)

Publication Number Publication Date
US20210376310A1 true US20210376310A1 (en) 2021-12-02

Family

ID=78704935

Family Applications (1)

Application Number Title Priority Date Filing Date
US17/333,485 Pending US20210376310A1 (en) 2020-05-29 2021-05-28 Atomic layer deposition of ionically conductive coatings for lithium battery fast charging

Country Status (5)

Country Link
US (1) US20210376310A1 (zh)
EP (1) EP4158715A2 (zh)
KR (1) KR20230018415A (zh)
CN (1) CN115836414A (zh)
WO (1) WO2021243163A2 (zh)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220025515A1 (en) * 2016-07-11 2022-01-27 Samsung Electronics Co., Ltd. Plasma-enhanced chemical vapor deposition apparatus and method of forming lithium-based film by using the same
US11264599B2 (en) * 2017-11-09 2022-03-01 Lg Energy Solution, Ltd. Electrode performance evaluation system and electrode performance evaluation method
CN114300671A (zh) * 2021-12-28 2022-04-08 蜂巢能源科技股份有限公司 一种石墨复合负极材料及其制备方法和应用
CN115224242A (zh) * 2022-06-13 2022-10-21 河南师范大学 一种锂电池正极片的制备方法及其应用
CN115295800A (zh) * 2022-10-09 2022-11-04 青岛龙迪碳材料科技有限公司 一种锂电池负极材料及其烧结制备方法
WO2023194710A1 (en) * 2022-04-04 2023-10-12 Ucl Business Ltd Solid electrolyte film
WO2023212229A1 (en) * 2022-04-27 2023-11-02 Board Of Trustees Of The University Of Arkansas High-energy lithium metal batteries enabling extremely fast charge and discharge

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023215476A1 (en) * 2022-05-04 2023-11-09 The Regents Of The University Of Michigan Artificial solid electrolyte interphase for enabling ethylene carbonate-free electrolytes in lithium-ion batteries

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170149050A1 (en) * 2014-06-23 2017-05-25 Shin-Etsu Chemical Co., Ltd. Negative electrode material for non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and method of producing negative electrode active material particles
US20200343554A1 (en) * 2018-01-26 2020-10-29 Panasonic Intellectual Property Management Co., Ltd. Electrode material and battery
US20220013764A1 (en) * 2018-11-30 2022-01-13 Panasonic Intellectual Property Management Co., Ltd. Electrochemical device negative electrode and electrochemical device, and method for manufacturing electrochemical device negative electrode and method for manufacturing electrochemical device

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006007863A1 (en) * 2004-07-16 2006-01-26 Cathingots Limited Electrolysis apparatus with solid electrolyte electrodes
US9570748B2 (en) * 2012-10-12 2017-02-14 Ut-Battelle, Llc Lipon coatings for high voltage and high temperature Li-ion battery cathodes
KR102425305B1 (ko) * 2014-05-27 2022-07-27 지앙수 헹트론 나노테크 컴퍼니 리미티드 개선된 리튬 금속 산화물 캐소드 물질 및 그의 제조 방법
PL3198669T3 (pl) * 2014-09-23 2024-03-04 Jiangsu Hengtron Nanotech Co., Ltd. Akumulatory o zwiększonej wydajności zawierające tlenek metalu litu
JP7115976B2 (ja) * 2015-08-28 2022-08-09 グループ１４・テクノロジーズ・インコーポレイテッド リチウムの非常に耐久性のある挿入を有する新規な材料およびその製造方法
KR20210018245A (ko) * 2018-04-30 2021-02-17 라이텐, 인코포레이티드 리튬 이온 배터리 및 배터리 물질
US20200028208A1 (en) * 2018-07-18 2020-01-23 The Regents Of The University Of Michigan System And Method For Atomic Layer Deposition Of Solid Electrolytes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170149050A1 (en) * 2014-06-23 2017-05-25 Shin-Etsu Chemical Co., Ltd. Negative electrode material for non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and method of producing negative electrode active material particles
US20200343554A1 (en) * 2018-01-26 2020-10-29 Panasonic Intellectual Property Management Co., Ltd. Electrode material and battery
US20220013764A1 (en) * 2018-11-30 2022-01-13 Panasonic Intellectual Property Management Co., Ltd. Electrochemical device negative electrode and electrochemical device, and method for manufacturing electrochemical device negative electrode and method for manufacturing electrochemical device

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Addressing Interfacial Issues in liquid-based and solid state batteries by atomic and molecular layer deposition; Yang Zhao Cell Press review; Joule;12/19/2018 (Year: 2018) *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220025515A1 (en) * 2016-07-11 2022-01-27 Samsung Electronics Co., Ltd. Plasma-enhanced chemical vapor deposition apparatus and method of forming lithium-based film by using the same
US11898244B2 (en) * 2016-07-11 2024-02-13 Samsung Electronics Co., Ltd. Plasma-enhanced chemical vapor deposition method of forming lithium-based film by using the same
US11264599B2 (en) * 2017-11-09 2022-03-01 Lg Energy Solution, Ltd. Electrode performance evaluation system and electrode performance evaluation method
CN114300671A (zh) * 2021-12-28 2022-04-08 蜂巢能源科技股份有限公司 一种石墨复合负极材料及其制备方法和应用
WO2023194710A1 (en) * 2022-04-04 2023-10-12 Ucl Business Ltd Solid electrolyte film
WO2023212229A1 (en) * 2022-04-27 2023-11-02 Board Of Trustees Of The University Of Arkansas High-energy lithium metal batteries enabling extremely fast charge and discharge
CN115224242A (zh) * 2022-06-13 2022-10-21 河南师范大学 一种锂电池正极片的制备方法及其应用
CN115295800A (zh) * 2022-10-09 2022-11-04 青岛龙迪碳材料科技有限公司 一种锂电池负极材料及其烧结制备方法

Also Published As

Publication number Publication date
EP4158715A2 (en) 2023-04-05
WO2021243163A3 (en) 2022-02-10
WO2021243163A2 (en) 2021-12-02
CN115836414A (zh) 2023-03-21
KR20230018415A (ko) 2023-02-07

Similar Documents

Publication Publication Date Title
US20210376310A1 (en) Atomic layer deposition of ionically conductive coatings for lithium battery fast charging
EP3540825B1 (en) Lithium secondary battery
US10608249B2 (en) Conformal coating of lithium anode via vapor deposition for rechargeable lithium ion batteries
Kazyak et al. Enabling 4C fast charging of lithium‐ion batteries by coating graphite with a solid‐state electrolyte
US10439212B2 (en) Aluminum borate coated lithium ion cathode materials
Lee et al. Leveraging titanium to enable silicon anodes in lithium‐ion batteries
Liang et al. Asymmetrically coated LAGP/PP/PVDF–HFP composite separator film and its effect on the improvement of NCM battery performance
US20180315995A1 (en) Method for manufacturing an accumulator of the lithium-ion type
Negi et al. Optimized atomic layer deposition of homogeneous, conductive Al 2 O 3 coatings for high-nickel NCM containing ready-to-use electrodes
EP3900101A1 (en) High efficiency electrolytes for high voltage battery systems
KR20190056139A (ko) 이차전지용 양극 활물질, 그 제조방법 및 이를 포함하는 리튬 이차전지
JP2015065000A (ja) 非水電解質二次電池及び電池パック
Zhao et al. Practical prelithiation of 4.5 V LiCoO2|| graphite batteries by a passivated lithium‐carbon composite
Ko et al. Lithium fluoride layer formed by thermal evaporation for stable lithium metal anode in rechargeable batteries
Kang et al. AgNO3-preplanted Li metal powder electrode: Preliminary formation of lithiophilic Ag and a Li3N-rich solid electrolyte interphase
EP3800713A1 (en) Cathode active material for lithium secondary battery and lithium secondary battery
EP3783708B1 (en) Positive electrode active material for lithium secondary battery and lithium secondary battery
KR20180037899A (ko) 이차전지용 양극활물질 및 이를 포함하는 이차전지
WO2023003654A2 (en) Sulfide coatings for ultra-stable cathodes of lithium batteries
Menkin et al. Towards an understanding of the SEI formation and lithium preferential plating on copper
WO2021168189A9 (en) High-performance microsized anodes and methods of making and using the same
Hornsveld Atomic layer deposition for Li-ion batteries: Novel chemistries, surface reactions and film properties
CN111129433A (zh) 用于从电化学电池中除去可能形成氢的化合物的方法
US20230361350A1 (en) Artificial Solid Electrolyte Interphase For Enabling Ethylene Carbonate-Free Electrolytes In Lithium-Ion Batteries
US20240055596A1 (en) Coated nickel-rich layered oxide electrodes and applications thereof

Legal Events

Date Code Title Description
STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

AS Assignment

Owner name: UNITED STATES DEPARTMENT OF ENERGY, DISTRICT OF COLUMBIA

Free format text: CONFIRMATORY LICENSE;ASSIGNOR:UNIVERSITY OF MICHIGAN;REEL/FRAME:064871/0456

Effective date: 20230116

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: FINAL REJECTION MAILED